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Publication numberUS4661217 A
Publication typeGrant
Application numberUS 06/895,173
Publication dateApr 28, 1987
Filing dateAug 11, 1986
Priority dateAug 17, 1985
Fee statusPaid
Also published asCA1275066A1, CN1013887B, CN86105208A, DE3529531A1, EP0212512A1, EP0212512B1
Publication number06895173, 895173, US 4661217 A, US 4661217A, US-A-4661217, US4661217 A, US4661217A
InventorsDieter Degner, Heinz Hannebaum, Michael Steiniger
Original AssigneeBasf Aktiengesellschaft
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Preparation of carbamic acid esters
US 4661217 A
Abstract
Carbamic acid esters (I)
R1 NHCOOR2                                       (I)
wherein R1 is H, alkyl, cycloalkyl or alkylaryl and R2 is alkyl, are prepared by electro-oxidation of a formamide (II)
R1 NHCHO                                              (II)
in the presence of an alcohol R2 OH and of an ionic halide.
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Claims(4)
We claim:
1. A process for the preparation of carbamic acid esters of the formula (I)
R1 NHCOOR2                                       (I),
where R1 is hydrogen, alkyl, cycloalkyl or alkaryl and R2 is low molecular weight alkyl, wherein a formamide of the formula (II)
R1 NHCHO                                              (II)
is oxidized electrochemically in the presence of an alcohol of the formula R2 OH and of an ionic halide.
2. A process as claimed in claim 1, wherein the halide used is a salt of hydrobromic acid.
3. A process as claimed in claim 1, wherein graphite anodes are used for the electrolysis.
4. A process as claimed in claim 1, wherein the alcohol used is methanol or ethanol.
Description

The present invention relates to a novel process for the preparation of carbamic acid esters.

As is generally known, carbamic acid esters have hitherto been prepared from phosgene by reaction with an alcohol to give a chloroformic acid ester followed by aminolysis. In industrial operation, the handling of the highly toxic and corrosive starting materials and intermediates requires considerable effort. Further, the processes generate HCl or halogen-containing waste salts, which, in industrial operation, are often very expensive to remove (cf. Ullmann, Enzyklopte, uml/a/ die der techn. Chemie, 9, 118 et seq.).

In alternative processes which do not employ phosgene, urea is reacted with alkanols. The disadvantages here are high reaction temperatures, long reaction times, and the technical difficulty of handling solids (compare, eg. Houben-Weyl, Methoden d. org. Chemie, 8, 111 et seq.).

It is an object of the present invention to provide a process for the preparation of carbamic acid esters which is technically simple and economical and environmentally particularly unobjectionable.

We have found that this object is achieved and that carbamic acid esters of the general formula (I)

R1 NHCOOR2                                       (I),

where R1 is hydrogen, alkyl, cycloalkyl or alkaryl and

R2 is low molecular weight alkyl, may be prepared particularly advantageously when a formamide of the general formula (II)

R1 NHCHO                                              (II)

is oxidized electrochemically in the presence of an alcohol of the formula R2 OH and of an ionic halide.

The success of the process is surprising since it has long been known that the electrochemical reaction of formamides in alcohols in the presence of conductive salts such as tetraalkylammonium tetrafluoroborate always leads to alkoxyformamides (compare, eg. L. Eberson and K. Nyberg, Tetrahedron 32 (1976), 2185-2206), as is made clear by the following equation: ##STR1##

The reaction according to the invention may be represented by the following equation: ##STR2##

In the starting material of the formula (II), R1 is hydrogen, alkyl, cycloalkyl or alkylaryl.

Preferred alkyl radicals are of 1 to 12, especially 1 to 8, more particularly 1 to 4, carbon atoms, eg. methyl, ethyl, n- and isopropyl, n-butyl and tert-butyl.

Preferred cycloalkyl radicals are of 3 to 8, especially 5 or 6, carbon atoms. R1 may also be alkylaryl of 7 to 12, especially 7 or 8, carbon atoms, eg. benzyl or phenylethyl.

The radicals mentioned may additionally carry substituents which are inert under the reaction conditions, for example C1 -C4 -alkyl or C1 -C4 -alkoxy, halogen or nitrile.

The reaction may be carried out, for example, using the following formamides: methylformamide, ethylformamide, n- and isopropylformamide, n-butylformamide, n-octylformamide, cyclohexylformamide, cyclopentylformamide, benzylformamide and unsubstituted formamide.

In the alcohols of the formula R2 OH, R2 is low molecular weight alkyl, especially alkyl of 1 to 5 carbon atoms, preferably methyl or ethyl. Examples of alcohols which may be used are n- and isopropanol, n-butanol, n-propanol and especially methanol and ethanol.

Suitable ionic halides are salts of hydriodic acid, hydrobromic acid and hydrochloric acid. Salts of hydrobromic acid, eg. alkali metal and alkaline earth metal bromides and quaternary ammonium bromides, especially tetraalkylammonium bromides, are particularly preferred. The cation is immaterial to the invention and it is therefore also possible to use other ionic metal halides, but the use of cheap halides is advantageous. Examples include sodium, potassium, calcium and ammonium bromides and dimethylammonium, trimethylammonium, tetramethylammonium and tetraethylammonium bromide.

The process according to the invention does not demand any particular electrolysis cell. It can advantageously be carried out in an unpartitioned continuous flow cell. The anode may consist of any conventional anode material which is stable under the electrolysis conditions, such as a noble metal, for example gold or platinum, or a metal oxide such as NiOx. The preferred anode material is graphite. The cathode may for example consist of metals, such as lead, iron, steel, nickel or a noble metal, eg. platinum. The preferred cathode material is, again, graphite.

The composition of the electrolyte may be selected within wide limits. For example, it may consist of

10-80% by weight of R1 NHCHO,

10-80% by weight of R2 OH and

0.1-10% by weight of halide.

If desired, a solvent may be added to the electrolyte, eg. to improve the solubility of the formamide or of the halide. Examples of such solvents are nitriles, eg. acetonitrile, carbonates, eg. dimethyl carbonate, and ethers, eg. tetrahydrofuran. The current density is not a limiting factor in the process according to the invention and is, eg., 1-25 A/dm2, preferably 3-12 A/dm2. If electrolysis is carried out under atmospheric pressure, the temperature is advantageously chosen to be at least 5-10 C. below the boiling point of the electrolyte. If methanol or ethanol is used, the elecytolysis is preferably carried out at 20-30 C. We have found, surprisingly, that the process according to the invention offers the possibility of high conversions of the formamides without deterioration in yield. The current yields are also exceptionally high in the process according to the invention. For example, complete conversion of the formamide is achieved when electrolyzing with only 2-2.5 F/mole of formamide.

The electrolysis products may be worked up by a conventional method. Advantageously, the electrolysis product is worked up by distillation. Excess alkanol and any co-solvent employed are first distilled off, the halides are removed in a conventional manner, for example by filtration or extraction, and the carbamic acid esters are purified by distillation or recrystallized. Alkanol, any unconverted formamide and co-solvent as well as halides can advantageously be recycled to the electrolysis. The process according to the invention may be carried out batchwise or continuously.

The carbamic acid esters produced by the process according to the invention are versatile intermediates in the synthesis of isocyanates, crop protection agents and assistants, for example for textile finishing.

EXAMPLES

The electro-oxidation was carried out in an unpartitioned electrolysis cell with graphite anodes and cathodes, at 20-25 C. During the electrolysis, the electrolyte, which contained sodium bromide as a conductive salt, was pumped through the cell via a heat exchanger at a rate of 200 liters/h. Table 1 shows the composition of the electrolyte.

After completion of the electrolysis, working up was effected by distilling off the alcohol under atmospheric pressure until the bottom temperature reached 120-130 C. and purifying the residue by distillation at 5-40 mbar. In the case of unsubstituted methyl carbamate (Example 7), the product was purified by recrystallization from ethyl acetate. In Examples 8 and 9, the residue after removing the alcohol was filtered hot at 80-100 C. to remove NaBr; thereafter the urethanes crystallized in a spectroscopically (1 H-NMR) pure form from the filtrate at 20-30 C. The carbamates were obtained in yields of 57-88%, based on starting material (II), at 100% conversion.

Examples 1 to 9 are summarized in Table 1.

                                  TABLE 1__________________________________________________________________________Electro-oxidation of formamides (II) to carbamic acid esters (I) ##STR3##                   Electrolyte II:          Starting material                   NaBr:R2 OH                            Number of                                  Amount of elec-                                           Current                                                   YieldtyExample R1      R2          (II) [g] [% by weight]                            electrodes                                  tricity [F/mole]                                           [A/dm2 ]                                                   [g] [%]__________________________________________________________________________1     CH3      CH3          390      15:1:84  6     2.5      3.3     477 812     CH3      CH3          390      15:2:83  6     2.5      6.7     519 883     CH3      C2 H5          390      15:1:84  6     2.5      3.3     481 714     C2 H5      CH3          375      15:1:84  11    2.8      3.3     414 785     i-C3 H7      CH3          300      10:1:89  6      2.25    3.3     314 786     n-C8 H17      CH3          300      15:1:84  6      2.25    3.3     285 807     H    CH3          260      15:1:84  9     2.5      3.3     247 578     C6 H11      CH3          603      16.4:0.7:82.9                            9     2.1      3.3     620 829     CH2 C6 H5      CH3          300      15:1:84  6     2.2      3.3     286 78__________________________________________________________________________
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3459643 *Feb 3, 1967Aug 5, 1969Sprague Electric CoAlkoxylation of n-methyl-n-hydrocarbylamides
US3464960 *Dec 15, 1967Sep 2, 1969Us ArmyMixture for rapid polymerization
US3941666 *Jul 18, 1974Mar 2, 1976Hoechst AktiengesellschaftProcess for the preparation of N-(α-alkoxyethyl)-carboxylic acid amides
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US4140593 *Aug 19, 1977Feb 20, 1979Hoechst Aktiengesellschaftω-Alkoxy derivatives of lactams and process for their manufacture
US4288300 *May 14, 1980Sep 8, 1981Hoechst AktiengesellschaftProcess for the manufacture of N-α-alkoxyethyl-carboxylic acid amides
US4430262 *Mar 11, 1982Feb 7, 1984Shell Oil CompanyPreparation of isocyanates and/or derivatives thereof
US4457813 *Mar 4, 1983Jul 3, 1984Monsanto CompanyElectrolysis cells and electrolytic processes
US4510024 *Oct 18, 1983Apr 9, 1985Mitsubishi Rayon Co., Ltd.Novel polymer composition
US4588482 *Jun 10, 1985May 13, 1986Basf AktiengesellschaftPreparation of phthalaldehyde acetals
US4612092 *Sep 27, 1985Sep 16, 1986Basf AktiengesellschaftPreparation of aromatic carboxylates
Non-Patent Citations
Reference
1 *Houben Weyl, Methoden d. org. Chemie, 8, 111 118.
2Houben--Weyl, Methoden d. org. Chemie, 8, 111-118.
3 *L. Eberson and K. Nyberg, Tetrahedron 32, (1976), 2185 2206.
4L. Eberson and K. Nyberg, Tetrahedron 32, (1976), 2185-2206.
5 *Shono et al. J. Am. Chem. Soc., 97, (1975), pp. 4264 4268.
6Shono et al. J. Am. Chem. Soc., 97, (1975), pp. 4264-4268.
7 *Ullmann, Enzyklop die der techn. Chemie, 9, 118 119.
8Ullmann, Enzyklopadie der techn. Chemie, 9, 118-119.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4759832 *Feb 13, 1987Jul 26, 1988Basf AktiengesellschaftPreparation of biscarbamates and novel biscarbamates
US5214169 *Apr 30, 1992May 25, 1993Merrell Dow Pharmaceuticals Inc.N-(2,3-epoxycyclopentyl) carbamate derivatives
Classifications
U.S. Classification205/435, 560/115, 560/24
International ClassificationC25B3/10, C25B3/02, C07C271/10
Cooperative ClassificationC25B3/02
European ClassificationC25B3/02
Legal Events
DateCodeEventDescription
Sep 25, 1998FPAYFee payment
Year of fee payment: 12
Sep 26, 1994FPAYFee payment
Year of fee payment: 8
Oct 1, 1990FPAYFee payment
Year of fee payment: 4
Dec 11, 1986ASAssignment
Owner name: BASF AKTIENGESELLSCHAFT, 6700 LUDWIGSHAFEN, RHEINL
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:DEGNER, DIETER;HANNEBAUM, HEINZ;STEINIGER, MICHAEL;REEL/FRAME:004644/0861
Effective date: 19860731
Owner name: BASF AKTIENGESELLSCHAFT, GERMANY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DEGNER, DIETER;HANNEBAUM, HEINZ;STEINIGER, MICHAEL;REEL/FRAME:004644/0861